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Metallic Character
 All the transition elements are metals; this is because the number of electrons in outermost
shell is only 2.
 Transition metals are hard, malleable and ductile due to presence of strong metallic bonds.
 Transition metals crystallize in all the three face centred cubic (fcc), hexagonal close packed
(hcp) and body centred cubic (bcc) crystals.
 Transition metals of VIII and IB Groups are softer and more ductile as compare to the other
transition metals.
 Along with metallic bonding, transition metals also show covalent bonding due to presence of
unfilled d-orbitals.
 As transition elements are metals so they good conductors of heat and electricity.

Melting and Boiling Point

 Transition metals usually have very high value of melting and boiling points due to presence
of strong metallic bonds.
 Zn, Cd and Hg metals have lower metaling and boiling points as they have completely filled d
orbitals because of which no unpaired electron is available. Because of unavailability of
unpaired electrons, these metals do not undergo covalent bonding. Rest of the transition
metals does have metallic as well as covalent bonding.
 Metals towards the middle of each transition series have highest melting point.?

Atomic (Covalent) and Ionic Radii

 The covalent radii of the elements decrease from left to right across a row in the transition
series. This is because of the poor screening by the d electrons due to which, the nuclear
charge attracts all of the electrons more strongly, hence a contraction in size occurs.
 The atomic radii for the elements from Cr to Cu are very close to one another. This closeness
in atomic radii is due to the shielding of outer 4s electrons by 3d electrons from the inward
pulls of nucleus. As a result of these two opposing effects, the atomic radii do not alter much
 on moving from Cr to Cu.

 The elements in the first group in the d-block show the excepted increase (due to the addition
of extra shell) in size Sc → Y → La. However in the subsequent groups there is an increase
between first and second members, but hardly any increase between second and third
elements. This is due to lanthanide contraction (discussed in f-block elements).

The ionization energy (IE)

 The first ionization energy of transition elements are higher than those of s-block elements but
lower than p-block elements.
 In a particular transition series, ionization energy although increases gradually as we move
from left to right but this increase is not appreciable.
 The increase in ionization energy is due to increase in nuclear charge, the effect of increase
in nuclear charge is partly balanced by the increase in screening effect. Consequently, the
increase in ionization energy along the period of d-block elements is very small.
 In transition elements, on moving along the period, the addition of the extra electron in the (n-
1) d level takes place. This electron provides a screening effect and shields the outer ns
electrons from the nucleus pull.
 Because of this shielding effect of d electrons, the effect of nuclear charge (effective nuclear
charge) on outer ns electrons is somewhat less than the actual nuclear charge.
 Thus the effects of the increasing nuclear charge and the shielding effect created due to the
expansion of (n-1)d orbital oppose each other.
 On account of these counter effects, the ionization potentials increase rather slowly on
moving in a period of the first transition series
First Ionization Energy
 The first ionization energy for the first four 3d series elements (Sc, Ti, V and Cr) arte almost
same i.e. differ only slightly from one another.
 The values of first ionization energy for Fe, Co, Ni and Cu are also very close to one another.
 The value of first ionization energy for Zn is considerably high due to extra-stability of
completely filled 3d10 level.
Second ionization energy
 The second ionization emerges increases more or less regularly with the increase of atomic
number.
 The value of second ionization energy for Cr and Cu are higher than those of their
neighbours. This is due to the fact that the electronic configurations of Cr+ and Cu+ ions have
extra stable 3d5 and 3d10 levels.
 There is a sudden fall in the values of ionization potentials in going from II B (Zn-group
elements) to IIIA sub-group. This is because in case of IIIA group elements the electron to be
removed is from a 4p-orbital which is incompletely filled, while in case of the II B group
elements, the electron to be removed is from completely filled 4s-orbital which required extra
energy

Colour
Many compounds of transition elements are coloured in contrasts to those of s and p block
elements.In compound state due to the surrounding groups (ligands), the d-orbitals of transition
elements are not degenerate but split into two groups of different energy.
Thus it is possible to promote electrons from one group to another group. This corresponds to
fairly small amount of energy difference and so light is absorbed in visible region. Some
compounds of transition metals are white, for example ZnSO4 and TiO2. In these compounds it is
not possible to promote the electrons within the d-level.

Formation of Alloys
Alloys are homogenous solid solutions of two or more metals obtained by melting the
components and then cooling the melt. These are formed by metals whose atomic radii differ by
not more than 15% so that the atoms of one metal can easily take up the positions in the crystal
lattice of the other. Since transition metals have similar atomic radii, they form alloys very readily.

Interstitial Compounds
 Sometimes transition metals form non stoichiometry compounds. These are compounds of
indefinite structure and proportions. For example Fe0.94O. It is mostly due to the variable
valency of transition elements. Sometimes, non-stoichiometry is caused by defects in the
solid structures.
 Transition metals form number of interstitial compounds, in which they take up atoms of small
size e.g. H, C and N in the vacant spaces in their lattices. The presence of these atoms result
in decrease in malleability and ductility of the metals but increases their tensile strength.

Variable Oxidation State

They show variable oxidation states unlike s and p block elements. The oxidation states changes
in units of one, e.g. Fe2+ and Fe+3, Cu+1 and Cu+2.
Scandium can have an oxidation number of (+II) if both s electrons are used for bonding and
(+III) when two s and one d electrons are involved. Similarly all the elements show variable
oxidation states depending upon the number of electrons available for bonding in their s and d
sub-shells.
Catalytic Property
Many transition metals and their compounds have catalytic properties. For e.g. V2O5, Fe, FeCl3,
Ni, Pd etc. This is due to following reasons
 Variable oxidation state: Due to variable oxidation state they form unstable intermediate
compounds and provide a new path with lower activation energy for the reaction (Intermediate
compound formation theory)
 Large Surface area: Finely divided transition metals or their compounds provide a large
surface area for adsorption and the adsorbed reactants react faster due to the closer contact.

Complex Formation
The transition elements have an unparalleled tendency to form coordination compounds with the
Lewis bases, which are called as ligands.
CO3+ + 6NH3 → [CO(NH3)6]3+
Fe2+ + 6CN– → [Fe(CN)6]4–
s and p block elements form very few complexes. The reason transition elements are so good at
forming complex is that they have small, highly charged ions and have vacant low energy orbitals
to accept lone pairs of electrons donated by ligands.

Transition Catalystic Action

element/compound
TiCl3 Used as Ziegler – Natta catalyst

V2O5 Converts SO2 to SO3 in the contact process for making

H2SO4
MnO2 Used as a catalyst to decompose KClO3 to give O2

Fe Used in Haber – Bosch process for making NH3

FeCl3 Production of CCl4 from CS2 and Cl2

FeSO4 & H2O2 Fenton’s reagent

PdCl2 Wacker process for the following conversion :C2H2 + H2O +

PdCl2 → CH3CHO + 2HCl + Pd
Pd For hydrogenation (Phenol → Cyclohexanone)

Pt/PtO Adams catalyst used for reduction

Pt SO2 → SO3 contact process

Cu In manufacture of (CH3)2SiCl2

Cu/V Oxidation of cyclohexanol

CuCl2 Deacon process for making Cl2 from HCl

Ni Raney nickel
Variable Oxidation State
Transition elements show variable oxidation states unlike s and p block elements.The oxidation
states changes in units of one, e.g. Fe2+ and Fe+3, Cu+1 and Cu+2.
Scandium can have an oxidation number of (+II) if both s electrons are used for bonding and
(+III) when two s and one d electrons are involved. Similarly all the elements show variable
oxidation states depending upon the number of electrons available for bonding in their s and d
sub-shells.
Transition metals have unique property to show variable oxidation state. This property arises
from the fact that the energy levels of 3d, 4d and 5d orbitals are very close to those of 4s, 5s and
6s orbitals respectively and, therefore, electrons from both ns and (n-1)d orbitals can be
used, infect they are used, for the formation and bonds by transition metals.
Minimum oxidation state: All the transition elements except Cr, Cu, Ag, Au and Hg which have
a minimum oxidation state of +1 exhibit a minimum oxidation state of +2.
Maximum oxidation state: Each of the elements in groups III B to VII B can show the maximum
oxidation state equal to its group number. For example, Cr in group VIB shows a maximum
oxidation state of +6 in Cr2O72– ion.
Most of the elements in VIII group show a maximum oxidation state equal to + 6.
However, Ru and Os have a maximum oxidation state equal to +8 which is the highest oxidation
state shown by any element.
Relative stability of various oxidation states:
 The relative stabilities of various oxidation states of 3d-series elements are due to the extra
stability of 3d0, 3d5 and 3d10configurations.
 Ti4+ (3d0) is more stable than Ti3+ (3d1)
 Mn2+ (3d5) is more stable than Mn4+ (3d4).
 The higher oxidation state of 4d and 5d series elements are generally more stable than those
of the elements of 3d series, e.g., Mo, Tc (4d series elements) and W, Re (5d-series
elements) s.
 The highest oxidation states of second and third row elements are encountered in compounds
containing the more electronegative elements viz. F, O and Cl

Magnetic Property
On the basis of behaviour in a magnetic field, substance are classified as paramagnetic,
diamagnetic and ferromagnetic. Those substance which are attracted by the applied magnetic
field are called paramagnetic where as those which are repelled by the magnetic field are called
diamagnetic. Substances which are very strongly attracted by the applied field are called
ferromagnetic.

Paramagnetism is a property due to the presence of unpaired electrons. Thus most of the
transition metals are paramagnetic. As the number of unpaired electrons increases, the
paramagnetic character also increases.

The magnetic moment is calculated from the following formula μ = √n(n+2) BM where n is the
number of unpaired electrons and B. M stands for Bohr magneton.
 Density
Because of small size of their atoms and strong metallic bonding the density and hardness of
transition elements are high.? Except for mercury, which is a liquid at room temperature all other
elements are solid metals exhibiting all the characteristics of a metal.

Illustrations
Question 1: K2PtCl6 is a well known compound whereas corresponding Ni compound is not known. State a
reason for it.
Solution: This is because Pt4+ is more stable than Ni4+ has the sum of four ionization energies of Pt is less than
that of Ni.
________________________________________________________________________
Question 2: Why do transition elements show variable oxidation states?
Solution: In the transition elements, the energies of (n-1)d orbitals and ns orbitals are very close. Hence
electrons from both can participate in bonding.
________________________________________________________________________
Question 3: Explain briefly how +2 state becomes more and more stable in the first half of the first row
transition elements with increasing atomic number.
or

Compare the stability of +2 oxidation state of the elements of the first transition series.
Solution: The sum IE1 + IE2 increases. As a result the standard reduction potentials (E0) becomes less and less
negative. Hence the tendency to form M2+ ion decreases. The greater stability of +2 state for Mn is due to half-
filled d-subshell (d5), that for zinc is due to completely filled d-subshell (d10) and half that for nickel is due to
highest negative enthalpy of hydration.
________________________________________________________________________
Question 4: Why Zn2+ salts are white while Ni2+ salts are blue?
Solution: Zn2+ has completely filled d-orbitals (3d10) while Ni2+ has incompletely filled d-orbitals (3d8).
________________________________________________________________________
Question 5: Why Zn2+ salts are white while Cu2+ salts are blue?
Solution: Reason same as above.
________________________________________________________________________
Question 6: Giving reasons indicate which one of the following would be coloured?
Cu+, VO2+, Sc3+, Ni2+ (At. Nos Cu = 29, V = 23, Sc = 21, Ni = 28)
Solution: Ni2+ due to incompletely filled d-orbitals.

Question 1: Transition elements..

a. form colourless compounds
b. do not form complexes
c. are metals and non metals both.
d. show variable oxidation states.
Question 2: Which of the following statements is incorrect?
a. Ti4+ is more stable than Ti3+
b. Mn2+ is more stable than Mn4+
c. The higher oxidation state of 3d series elements are generally more stable than those of the
elements of 5d series.
d. The highest oxidation states of second and third row elements are encountered in compounds
containing the more electronegative elements
Question 3: CO3+ + 6NH3 →
a. [CO(NH3)3]3+
b. [CO(NH3)5]2+
c. [CO(NH3)6]3+
d. [CO(NH3)2]2+
Question 4: Which of the following statements is incorrect?
a. All the transition elements are metals
b. Transition metals are hard, malleable and ductile due to presence of strong metallic bonds.
c. Transition metals crystallize in all the three face centred cubic (fcc), hexagonal close packed
(hcp) and body centred cubic (bcc) crystals.
d. Transition metals of VIII and IB Groups are harder and less ductile as compare to the other
transition metals.

Q.1 Q.2 Q.3 Q.4

d c c d